Substituted m-trifluoromethylphenylurea derivatives

ABSTRACT

1. A SUBSTITUTED M-TRIFLUOROMETHYLPHENYLUREA DERIVATIVE OF THE FORMULA   F3C-(1,3-PHENYLENE)-N(-CH2-X-R1)-CO-N(-R3)-CH3   WHERE R1 DENOTES THE RADICAL   R3-CO-   R3 DENOTES LOWER ALKYL, PHENYL OR BENZYL, X DENOTES OXYGEN, AND R2 DENOTES ALKYL OF 1 TO 3 CARBON ATOMS, METHOXY OR HYDROGEN.

United States Patent 3,847,971 SUBSTITUTED m-TRIFLUOROMETHYLPHENYL- UREA DERIVATIVES Karl-Heinz Koenig, Frankenthal, Rudolf Kolbinger,

Speyer, and Adolph Fischer, Mutterstadt, Germany, assignors to Badische Anilin- & Soda-Fabrik Aktiengesell. schaft, Ludwigshafen (Rhine), Germany No Drawing. Filed Jan. 5, 1972, Ser. No. 215,664 Claims priority, application Germany, Jan. 15, 1971, P 21 01 698.8 Int. Cl. C07c 127/20, 127/22, 153/07 US. Cl. 260-490 2 Claims ABSTRACT OF THE DISCLOSURE New and valuable substituted m-trifiuoromethylphenylurea derivatives having a good herbicidal action; herbicides containing these compounds as active ingredients; and a process for controlling the growth of unwanted plants with these compounds.

The present invention relates to new and valuable substituted m-trifiuoromethylphenylurea derivatives having a good herbicidal action and the use of these compounds as herbicides.

It is known to use m-trifiuoromethylphenylurea derivatives, e.g. N-m-trifiuoromethylphenyl-N',N-dimethylurea, as herbicides. However, their action is not satisfactory.

We have now found that substituted m-trifiuoromethylphenylurea derivatives of the formula where R denotes alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aryl or the radical 3,847,971 Patented Nov. 12, 1974 sion, emulsion or dust, may be applied by treating the unwanted plants, direct, or the soil in which the growth of unwanted plants is to be prevented.

The ureas may be synthesized by reacting the N-m-trifluoromethylphenyl-N-a-methylether (or thioether or acyloxy)-carbamoyl chlorides with appropriate primary or secondary amines.

The starting material for the substituted carbamyl chloride is N-m-trifluoromethylphenyl N chloromethylcarbamyl chloride. The latter is produced in two stages. In the first stage m-trifluoromethylaniline is reacted with paraformaldehyde, and in the second the hexahydrotriazine or N-methylene-(m-trifluoromethylaniline) formed is phosgenated. The N-m-trifluoromethylphenyl-N-a-methylether (or thioether or acyloxy)-carbamyl chlorides are obtained by reacting N-m-trifiuoromethylphenyl-N-chloromethylcarbamyl chlorides with the appropriate alcohols, mercaptans or carboxylic acids.

EXAMPLE 1 Preparation of N-m-trifluoromethylphenyl-N-methoxyrnethyl-N,N-dimethylurea 322 parts (by weight) of m-trifluoromethylaniline and 120 parts of paraformaldehyde are boiled under reflux in 200 parts of benzene. The water which forms is removed. When the reaction is over and no more water is formed, the reaction mixture is distilled in a water jet vacuum up to a bottoms temperature of C. In this manner the 1,3,S-tri-(m-trifluoromethylphenyl) hexahydrotriazine is obtained.

At 0 C., 2 moles of phosgene in 50 parts of chloroform is placed in a vessel and, at 0 C., a solution of 1 mole of 1,3,5-tri-(m-trifiuoromethylphenyl)-hexahydrotri-azine and 50 parts of chloroform is added. The reaction product is allowed to heat up slowly to room temperature and it is then boiled under reflux for 2 to 3 hours. The solvent is distilled OE and the residue fractionated. The yield is 45%; boiling point (0.5 mm.) C. In this manner N-m-trifiuoromethylphenyl N chloromethylcarbamyl chloride is obtained.

1 mole of N-m-trifiuoromethylphenyl N chloromethylcarbamyl chloride and 6 moles of methanol are stirred for 5 hours at 50 C., while passing through nitrogen. The mixture is stirred overnight, nitrogen still being passed in. Subsequently, excess methanol is distilled off and the residue fractionated. The yield is at least 90%, the boil ing point (0.3 mm. Hg) 98 C, In this manner N-m-trifluoromethylphenyl-N-methoxymethylcarbamoyl chloride is obtained.

The following carbamyl chlorides may be prepared analogously.

TABLE 1 N-C Q o CHz-X-Ra Molecular X Ii. Formula Weight, 13.1. or M.P. C.)

O CH: CnHxaClFaNOz 295.5 0.5 mm. Hg, 122-124.

0 *CH:CECH CrzHrsClFaNOg 291. 5 0.3 mm. Hg, 116-118.

0 -CHzOH(CHz)aCH| CnHzsClFaNOa 265.5 0.3 mm. Hg, 148-150.

( 32H&

0 (C2H) n OHI CzrHzrClFaNO: 421. 5 0.4 mm. Hg, 154-156.

CiaHuClFzNO: 335. 5 0.5 mm. Hg, 139-142.

TABLE 1Continued Molecular X R1 Formula Weight B: P. or M.P. (G.)

lfl llclFaNoi 343.5 0.3mm. Hg, 144-145.

O CuHisClFaNO: 357. 5 0.3 mm, Hg, 152-153.

0 015110011 3110, 320.5 0.1 mm. Hg, 143.

S -CHs CmHaClFzNOS 233.5 0.4 mm. Hg, 108-110.

B -(CH1).1GH1 CnHarOlFgNOS 431.5 0.5 mm. Hg, 160-161.

car bamyl chloride While passing nitrogen. The mixture is heated for 4 hours at 80 to 85 C. and subsequently distilled. There is obtained parts of N-acetoxymethyl-N- (m trifluoromethylphenyl) carbamyl chloride of the formula CHz-O-C O CH:

\COCI on Boiling point (0.05 mm. Hg): 119 to 122 C.

0.1 mole of 0,N-dimethylhydroxylamine hydrochloride is dissolved in 30 ml. of water. 70 ml. of chloroform is then added. At 10' C., a solution of 0.1 mole of NaOH in 16 ml. of water is dripped in and subsequently, also at 10 C., 0.1 mole of N m trifiuoromethylphenyl N methoxymethylcarbamyl chloride. After stirring for 2 hours, the chloroform layer is separated, the solvent is distilled off and the residue is fractionally distilled. There is thus obtained N m trifluoromethylphenyl N methoxymethyl N' methyl N methoxyurea; boiling point (0.05 mm. Hg): 91 to 94 C.

EXAMPLE 3 At 70 C., 72 g. of acetic acid is dripped into 54.4 parts of N chloromethyl N (m-trifluoromethyl henyn- TABLE 2 O CH; Q-

t F CHg-X-R Molecular X R R Formula Weight B.P. or M.P. 0.]

S 8%: 8 3a. $012108; 53% 381%: 55:85:53.- 0 CH2CE CH CH; cnH sFaNzoz 300 0.01 mm. Hg, 84.

I 0 CH; C17H23F Nz0z 344 0.02 mm. Hg, 108-110.

0 -CH H C11H13F3N202 262 0.01 mm. Hg, 111-113. 0 H nHnFaNzOz 338 0.05 mm. Hg, 112-114.

0 CH CH: Cl8Hl0F3N202 352 0.02 mm. Hg, 102-103. 0 -(CH2)1 CH CH; C23H 7F3N202 0.01 mm. Hg, 124-127. 0 3 3 14H1QF3N20, 304 0.01 mm. Hg, 99-101.

, CHJ

0 2Hs 3 laHflFaNzOe 290 0.02 mm. Hg, 89-92.

EXAMPLE 2 0 100 parts of cyclohexane and 5 parts of dimethylamine are placed in a vessel. At room temperature, 14 parts of N acetoxymethyl N (m trifluoromethylphenyl)- carbamyl chloride is dripped into the mixture, which is then stirred overnight. Water is added to the reaction product, the whole thoroughly stirred, and the organic phase is separated, dried and distilled. There is obtained 6.5 parts of N acetoxymethyl N (m trifluoromethylphenyl)- N-dimethylurea of the formula Boiling point (0.1 mm. Hg): 133 to 135 C.

TABLE 3 h) /CH:

(EH: R C F;

X-C O--R Molecular X R R Formula Weight B.P. or M.P. C.]

S OH: CH: CuHuFaNzOzS 320 0.01 mm. Hg, 140-144. -CH2CH: OCH: C14H11F3N2O4 334 0.02 mm. Hg, 145-147. 0 'C (CH3): CH3 Ci0H21FsN20a 346 Viscous, nondistillable Oil.

0 Q CH: Cn nFaNzOa 366 D0.

0 -CH3 H CrzHraFaNzOa 290 0.01 mm. Hg, 148-150.

CH CmHwFaNzO: 380 Viscous, nondistillable oil.

These urea types can only be distilled in a very high vacuum as otherwise they decompose easily.

We have found that, surprisingly, the strong herbicidal action is not essentially dependent on the type of the substituent R The herbicides according to the invention may be used as solutions, emulsions, suspensions or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, hydrocarbons having boiling points higher than 150 C., e.g. tetrahydronaphthalene or alkylated naphthalenes, or organic liquids having boiling points higher than 150 C. and having one or more than one functional group, e.g. the keto group, the ether group, the ester group or the amide group, this group or these groups being attached as substituent(s) to a hydrocarbon chain or being a component of a heterocyclic ring, may be used as spray liquids.

Aqueous formulations may be prepared from emulsion concentrates, pastes or wettable powders by adding water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means of wetting or dispersing agents, e.g.

polyethylene oxide adducts. Concentrates which are suitable for dilution with Water may be prepared from active ingredient, emulsifying or dispersing agent and possibly solvent. Oils may also be used to produce an oil dispersion.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier, e.g. kieselguhr, talc, clay or fertilizers.

The following examples demonstrate the use of the new active ingredients.

EXAMPLE 4 In a greenhouse, loamy sandy soil was filled into pots and sown with the seeds of Gossypium hirsutum, Echinochloa crus-galli, Poa annua, Poa trivialis and Chenopodium album.

The soil was then treated with 2 kg. per hectare of each of the following active ingredients, each bein dispersed and, for comparison,

IV. N-m-trifluoromethylphenyl-N',N'-dimethylurea After 4 to 5 weeks it was ascertained that active ingredients I, II and III had a stronger herbicidal action than IV.

The results of this experiment are given in the following table.

Active ingredient I II III IV Crop plant: Gossypium hirsutum 0 0 0 0 Unwanted plants:

Echinochloa crus-galli 86 98 87 Poa ammo 95 97 92 Poa trivialz's 90 98 90 80 Chenopodium album 97 100 97 NOTE.O=IIO damage; =complete destruction.

EXAMPLE 5 The plants Triticum vulgare, Echinochloa crus-galli, Poa annua, Poa trivialis, Chenopodium album and Szlnapis arvensis were treated at a growth height of 6 to 18 cm. with 1.5 kg. per hectare of each of I, II, III and IV, each active ingredient being dispersed in 500 liters of water per hectare. After 3 to 4 weeks it was ascertained that I, II and III had a stronger herbicidal action than IV on the broadleaved and grassy weeds.

The results of this experiment are given in the following table:

Active ingredient I II III IV Crop plant: Triticum vulgare 5 5 0 5 Unwanted plants:

Echinochloa crus-qalli. 92 97 94 85 Poa annua 90 96 92 82 Poa trivialis 93 96 91 80 Chenopodzum album. 98 97 97 95 Sinapis arvensis 99 98 98 95 N 0'1E.0=no damage; 100=eomplete destruction.

EXAMPLE 6 Plots were sown with Chenopodium album, Szlnapz's arvensis, Cyperus esculentus, Echinochloa crus-galli, L0- lium multiflorum, Dactylis glomerata and Setaria viridis. Subsequently the plots were treated with 4 kg. per hectare of each of I, II and III, each active ingredient being dispersed in 500 liters of water per hectare. After weeks it was ascertained that the plants were completely withered.

EXAMPLE 8 90 parts by weight of compound I is mixed with parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 9 parts by weight of compound II is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesultonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 10 20 parts by weight of compound IH is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 11 20 parts by weight of compound I is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280 C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 12 20 parts by weight of compound II is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphtha- 8 lene-a-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 13 3 parts by weight of compound III is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3 by weight of the active ingredient.

EXAMPLE 14 30 parts by weight of compound I is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of parafiin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

We claim:

1. A substituted m-trifluoromethylphenylurea derivative of the formula (u) /CHa @a- -r OH, R? C F: l

where R denotes the radical R denotes lower alkyl, phenyl or benzyl, X denotes oxygen, and R denotes alkyl of 1 to 3 carbon atoms, methoxy or hydrogen.

2. N acetoxymethyl N (m-trifluoromethylphenyD- N,N-dimethylurea.

References Cited Chem. Abstracts; 5-4: 19594b.

Chem. Abstracts; 53: 3764b. Chem. Abstracts; 963853.

VIVIAN GARNER, Primary Examiner US. Cl. X.R. 260-453 R, 455 R, 476 R, 544 C, 553 A; 71-98, 100, 106, 107,

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,847,971

DATED November 12, 1974 INVENTOR(S) Karl-Heinz Koenig, Rudolf Kolbinger and Adolf Fischer It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, in the formula under TABLE I, delete the bottom line "CH -X-R and insert-CH XR Column 2, the third molecular weight under TABLE I,

delete "265.5" and insert365.5--;

Column 2, in the fourth example under the column R in the TABLE I, delete "-(C H) CH and insert(CH -CH Column 4, line 17, delete "passing nitrogen." and insertpassing through nitrogen.-.

Signed and Scaled this twenty-eight Day Of October 1975 [S AL] A ttes t:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofParenIs and Trademarks 

1. A SUBSTITUTED M-TRIFLUOROMETHYLPHENYLUREA DERIVATIVE OF THE FORMULA 